Search Results (27)

Slow reaction kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) under alkaline conditions limits the performance of anion exchange membrane fuel cells and water electrolysers (AEMFC and AEMWE). Consequently, high loadings of PGM metal-based compounds such as Pd-CeO₂ and PtRu are required to obtain competitive performance. The amount of precious metals present can be reduced by exploiting interaction with an active support material that tunes both hydrogen desorption and hydroxyl adsorption, processes that are key descriptors of HOR activity. In this work, NiWO_3−xC is prepared, composed of oxygen-deficient tungsten oxide (WO_3−x) doped with Ni nanoparticles and mixed with conductive carbon (50:50 wt%). This material is decorated with Pd nanoparticles (6.6 wt% Pd loading). Structural analysis (XRD, XPS, and HR-TEM/STEM) confirm a hybrid morphology of Pd nanoparticles deposited on both the Ni and W portions of the support. The HOR and HER activity was studied using electrochemical tests and compared to the performance of both a Pd/C standard with equivalent Pd loading (6.9 wt%) and the NiWO_3−xC support. The Pd-normalized exchange current densities for the HOR (I⁰) are 18.7 A g_Pd⁻¹ for Pd/NiWO_3−xC and 3.21 A g⁻¹ for Pd/C. The enhanced HOR activity of Pd/NiWO_3−xC translates to high power densities in AEM fuel cell tests with this catalyst applied to the anode electrode (up to 0.9 W cm⁻²). Full article

In recent years CO₂ reforming of methane has attracted great interest as it produces high CO/H₂ ratio syngas suitable for the synthesis of higher hydrocarbons and oxygenated derivatives since it is a way for disposing and recycling two greenhouse gases with high environmental impact, CH₄ and CO₂, and because it is regarded as a potential route to store and transmit energy due to its strong endothermic effect. Along with noble metals, all the group VIII metals except for osmium have been studied for catalytic CO₂ reforming of methane. It was found that the catalytic activity of Ni, though lower than those of Ru and Rh, was higher than the catalytic activities of Pt and Pd. Although noble metals have been proven to be insensitive to coke, the high cost and restricted availability limit their use in this process. It is therefore valuable to develop stable Ni-based catalysts. In this contribution, we show how their activity and coking resistivity are greatly related to the size and dispersion of Ni particles. Well-dispersed Ni nanoparticles were achieved by multistep impregnation on a mesoporous silica support, namely SBA-15, obtained through a sol-gel method, using acetate as a nickel precursor and keeping the Ni loading between 5% and 11%. Significant catalytic activity was obtained at temperatures as low as 450 °C, a temperature well below their deactivation temperature, i.e., 700 °C. For the pre-reduced samples, a CO₂ conversion higher than 99% was obtained at approximately 680 °C. As such, their deactivation by sintering and coke formation was prevented. To the best of our knowledge, no Ni-based catalysts with complete CO₂ conversion at temperatures lower than 800 °C have been reported so far. Full article

The design of efficient hydrogen evolution reaction (HER) catalysts to minimize reaction overpotentials plays a pivotal role in advancing water electrolysis and clean energy solutions. Ru-based catalysts, regarded as potential replacements for Pt-based catalysts, face stability challenges during catalytic process. The precise regulation of metal–support interactions effectively prevents Ru nanoparticle degradation while optimizing interfacial electronic properties, enabling the simultaneous enhancement of catalytic activity and stability. Herein, we design an amorphous/crystalline support and employ in situ replacement to develop a Ru-NiP_x-Ni structure. The crystalline Ni phase with ordered atomic arrangement ensures efficient charge transport, while the amorphous phase with unsaturated dangling bonds provides abundant anchoring sites for Ru nanoclusters. This synergistic structure significantly enhances HER performance, which attains overpotentials of 19 mV at 10 mA cm⁻² and 70 mV at 100 mA cm⁻² in 1 m KOH, with sustained operation exceeding 55 h at 100 mA cm⁻². Electrochemical impedance spectroscopy analysis confirms that the Ru-NiP_x-Ni structure not only has a high density of active centers for HER, but also reduces the charge transfer resistance at the electrode–electrolyte interface, which effectively enhances HER kinetics. This study presents new directions for designing high-efficiency HER catalysts. Full article

Designing efficient and cost-effective electrocatalysts is crucial for the large-scale development of sustainable hydrogen energy. Amorphous catalysts hold great promise for application due to their structural flexibility and high exposure of active sites. We report a novel method for the in situ growth of amorphous CoNiRuO_x nanoparticle structures (CoNiRuO_x/NF) on a nickel foam substrate. In 1 m KOH, CoNiRuO_x/NF achieves a current density of 10 mA/cm² with a hydrogen evolution reaction (HER) overpotential of only 43 mV and remains stable for over 100 h at a current density of 100 mA/cm². An alkaline electrolyzer assembled with CoNiRuO_x/NF as the cathode delivers a current density 2.97 times higher than that of an IrO₂||Pt/C electrode pair at the potential of 2 V and exhibits excellent long-term durability exceeding 100 h. Experimental results reveal that the combined replacement and corrosion reactions facilitate the formation of the amorphous CoNiRuO_x structure. This work provides valuable insights for developing efficient and scalable amorphous catalysts. Full article

CO selective methanation is regarded as an efficient technological solution for hydrogen-rich gas purification in fuel cells. In this study, a series of bimetallic catalysts (Ru-Ni/xTiO₂-MgAl₂O₄) were synthesized by impregnation method after surface modification of MgAl₂O₄ supports with different contents of TiO₂. The prepared catalysts were characterized by XRD, BET, SEM, TEM, H₂-TPR, CO-TPD, NH₃-TPD, and XPS. The Ru-Ni/10TiO₂-MgAl₂O₄ exhibited excellent CO-SMET performance, removing the CO in the H₂-rich gas to less than 10 ppm with the selectivity above 50% in a temperature window range of 210–280 °C. The results showed that the TiO₂-modified MgAl₂O₄ support not only improved the interaction between metal and support, and promoted the dispersion of active component nanoparticles on the support, but also introduced oxygen vacancies or defects in the catalyst and enhanced the acidity, resulting in better catalytic activity and stability. Full article

In this study, we investigate the electrodeposition of various metals on silicon. Mn, Co, Ni, Ru, Pd, Rh, and Pt were identified as promising candidates for controlled electrodeposition onto silicon. Electrochemical evaluations employing cyclic voltammetry, Scanning Electron Microscopy (SEM) associated with energy-dispersive X-Ray Spectroscopy (SEM-EDS), and X-Ray Photoelectron Spectroscopy (XPS) techniques confirmed the deposition of Pd, Rh, and Pt as nanoparticles. Multi-cycle charge-controlled depositions were subsequently performed to evaluate the possibility of achieving tunable electrodeposition of nanostructured rhodium on n-doped silicon. The procedure increased surface coverage from 9% to 84%, with the average particle size diameter ranging from 57 nm to 168 nm, and with an equivalent thickness of the deposits up to 43.9 nm, varying the number of charge-controlled deposition cycles. The electrodeposition of rhodium on silicon presents numerous opportunities across various scientific and technological domains, driving innovation and enhancing the performance of devices and materials used in catalysis, electronics, solar cells, fuel cells, and sensing. Full article

This work aims at the effects of anion-exchange membranes (AEMs) and ionomer binders on the catalyst electrodes for anion-exchange membrane fuel cells (AEMFCs). In the experiments, four metal catalysts (nano-grade Pt, PtRu, PdNi and Ag), four AEMs (aQAPS-S8, AT-1, X37-50T and X37-50RT) and two alkaline ionomers (aQAPS-S14 and XB-7) were used. They were verified through several technical parameters examination and cell performance comparison for the optimal selection of AMEs. The bimetallic PdNi nanoparticles (PdNi/C) loaded with Vulcan XC-72R carbon black were used as anode electrodes by using the wet impregnation method, and Ag nanoparticles (Ag/C) were used as the catalyst cathode. It was found that the power density and current density of the X37-50RT are higher than the other three membranes. Also, alkaline ionomers of XB-7 had better performance than aQAPS-S14. The efficiency was improved by 32%, 155% and 27%, respectively, when compared to other membranes by using the same catalyst of PdNi/C, Ag/C and Pt/C. The results are consistent with the membrane ion conductivity measurements, which showed that the conductivity of the X37-50RT membrane is the highest among them. The conductivity values for hydroxide ions (OH⁻) and bromide ions (Br⁻) are 131 mS/cm and 91 mS/cm, respectively. These findings suggest that the properties (water uptake, swelling rate and mechanical) of the anion-exchange membrane (AEM) can serve as a key reference for AEM fuel cell applications. Full article

Tuning the chemical and structural environment of Ru-based nanomaterials is a major challenge for achieving active and stable hydrogen evolution reaction (HER) electrocatalysis. Here, we anchored ultrafine Ru nanoparticles (with a size of ~4.2 nm) on a hierarchical Ni₂P array (Ru/Ni₂P) to enable highly efficient HER. The Ni₂P promoter weakened the adsorption of proton on Ru sites by accepting electrons from Ru nanoparticles. Moreover, the hierarchical Ni₂P endowed Ru catalysts with a large surface area and stable open structure. Consequently, the as-fabricated Ru/Ni₂P electrode displayed a low overpotential of 57 and 164 mV at the HER current densities of 10 and 50 mA cm⁻², respectively, comparable to the state-of-the-art Pt catalysts. Moreover, the Ru/Ni₂P electrode can operate stably for 96 h at 50 mA cm⁻² without performance degradation. After pairing with a commercial RuO₂ anode, the Ru/Ni₂P anode catalyzed overall water splitting at 1.73 V with a current density of 10 mA cm⁻², which was 0.16 V lower than its commercial Ni counterpart. In situ Raman studies further revealed the optimized proton adsorption at the Ru-active sites on Ni₂P promoter, thus enhancing the electrocatalytic HER performance. Full article

CO-selective methanation (CO-SMET) is an efficient hydrogen-rich (H₂-rich) gas purification technology for proton exchange membrane fuel cells. It is vital to develop suitable catalysts with good low-temperature activity for CO-SMET reactions. In this study, RuNi/TiZr_x-mixed metal oxide (RuNi/TiZr_x-MMO) catalysts with different molar ratios of Zr/Ti, derived from a Zr-promoted NiTi-layered double hydroxide (NiTi-LDH) precursor were successfully prepared using the co-precipitation and wet impregnation methods. The RuNi/TiZr_0.2-MMO catalyst possesses higher catalytic performance in a lower temperature window of 180–280 °C, which can reduce the CO concentration to be below 10 ppm. The characterization results obtained from XRD, BET, SEM, TEM, XPS, TPR, and TPD suggest that the addition of ZrO₂ increases the surface area of the catalyst, improves the dispersion of metallic nanoparticles, increases the reducibility of Ni species on the RuNi/TiZr_0.2-MMO catalyst’s surface, and enhances the adsorption and activation ability of CO, resulting in remarkable catalytic performance at lower reaction temperatures. Moreover, the RuNi/TiZr_0.2-MMO catalyst demonstrated long-term catalytic stability and carbon resistance. Full article

This review extensively discusses current developments in bimetallic nanoparticle–GO and bimetallic nanoparticle–MOF nanocomposites as potential catalysts for HER, along with their different synthesis methodologies, structural characteristics, and catalytic mechanisms. The photoelectrocatalytic performance of these catalysts was also compared based on parameters such as Tafel slope, current density, onset potential, turnover frequency, hydrogen yield, activation energy, stability, and durability. The review shows that the commonly used metal alloys in the bimetallic nanoparticle–GO-based catalysts for HERs include Pt-based alloys (e.g., PtNi, PtCo, PtCu, PtAu, PtSn), Pd-based alloys (e.g., PdAu, PdAg, PdPt) or other combinations, such as AuNi, AuRu, etc., while the most used electrolyte sources are H₂SO₄ and KOH. For the bimetallic nanoparticle MOF-based catalysts, Pt-based alloys (e.g., PtNi, PtCu), Pd-based alloys (e.g., PdAg, PdCu, PdCr), and Ni-based alloys (e.g., NiMo, NiTi, NiAg, NiCo) took the lead, with KOH being the most frequently used electrolyte source. Lastly, the review addresses challenges and prospects, highlighting opportunities for further optimization and technological integration of the catalysts as promising alternative photo/electrocatalysts for future hydrogen production and storage. Full article

The development of direct dimethyl ether (DME) solid oxide fuel cells (SOFCs) has several drawbacks, due to the low catalytic activity and carbon deposition of conventional Ni–zirconia-based anodes. In the present study, the insertion of 2.0 wt.% Ru-Ce_0.7Zr_0.3O_2−δ (ruthenium–zirconium-doped ceria, Ru-CZO) as an anode catalyst layer (ACL) is proposed to be a promising solution. For this purpose, the CZO powder was prepared by the sol–gel synthesis method, and subsequently, nanoparticles of Ru (1.0–2.0 wt.%) were synthesized by the impregnation method and calcination. The catalyst powder was characterized by BET-specific surface area, X-ray diffraction (XRD), field emission scanning electron microscopy with an energy-dispersive spectroscopy detector (FESEM-EDS), and transmission electron microscopy (TEM) techniques. Afterward, the catalytic activity of Ru-CZO catalyst was studied using DME partial oxidation. Finally, button anode-supported SOFCs with Ru-CZO ACL were prepared, depositing Ru-CZO onto the anode support and using an annealing process. The effect of ACL on the electrochemical performance of cells was investigated under a DME and air mixture at 750 °C. The results showed a high dispersion of Ru in the CZO solid solution, which provided a complete DME conversion and high yields of H₂ and CO at 750 °C. As a result, 2.0 wt.% Ru-CZO ACL enhanced the cell performance by more than 20% at 750 °C. The post-test analysis of cells with ACL proved a remarkable resistance of Ru-CZO ACL to carbon deposition compared to the reference cell, evidencing the potential application of Ru-CZO as a catalyst as well as an ACL for direct DME SOFCs. Full article

Single-atom catalysts anchored to oxide or carbonaceous substances are typically tightly coordinated by oxygen or heteroatoms, which certainly impact their electronic structure and coordination environment, thereby affecting their catalytic activity. In this study, we prepared a stable oxygen evolution reaction (OER) catalyst on tungsten carbide using a simple pyrolysis method. The unique structure of tungsten carbide allows the atomic RuNi catalytic site to weakly bond to the surface W and C atoms. XRD patterns and HRTEM images of the WCx-RuNi showed the characteristics of phase-pure WC and W₂C, and the absence of nanoparticles. Combined with XPS, the atomic dispersion of Ru/Ni in the catalyst was confirmed. The catalyst exhibits excellent catalytic ability, with a low overpotential of 330 mV at 50 mA/cm² in 1 m KOH solutions, and demonstrates high long-term stability. This high OER activity is ascribed to the synergistic action of metal Ru/Ni atoms with double monomers. The addition of Ni increases the state density of WCx-RuNi near the Fermi level, promoting the adsorption of oxygen-containing intermediates and enhancing electron exchange. The larger proximity of the d band center to the Fermi level suggests a strong interaction between the d electrons and the valence or conduction band, facilitating charge transfer. Our research offers a promising avenue for reasonable utilization of inexpensive and durable WCx carrier-supported metal single-atom catalysts for electrochemical catalysis. Full article

In this study, Ni-Fe alloy nanoparticles were prepared using the proteic sol–gel method, followed by a reduction in H₂ at 500 and 700 °C, namely hereafter as NiFe-500 and NiFe-700, respectively. The morphological, structural, and magnetic properties were tuned via the thermal treatment in H₂. The samples were studied using XPS, TEM, Mössbauer spectroscopy, DC magnetic measurements, and electrochemical measurements. Ritveld refinements showed that the sample NiFe-500 has FCC (face-centered cubic) and BCC (body-centered cubic) NiFe alloys, while the sample NiFe-700 has only FCC NiFe alloy. For both samples, magnetization measurements in the range of 300–900 K showed the presence of the Griffiths phase, indicating the formation of clusters of either Fe or Ni-Fe alloys rich in Fe. The sample NiFe-500 presented ferromagnetic (FM) transitions at 533, 700, and 834 K, assigned to the alloys Ni₃₇Fe₆₃-FCC, Ni₄₆Fe₅₄-FCC, and Ni₅₅Fe₄₅-FCC, respectively. In contrast, we could not observe the FM transition of the BCC Ni-Fe alloy because of limitations in our experimental setup (T ≤ 900 K). Meanwhile, three FM transitions were observed for the sample NiFe-700 at 480, 655, and 825 K, attributed to the alloys Ni₃₄Fe₆₆-FCC, Ni₄₃Fe₅₇-FCC, and Ni₅₄Fe₄₆-FCC, respectively. At 5 K, the samples NiFe-500 and NiFe-700 have saturation magnetizations of 164.2 and 173.6 emu g⁻¹, respectively. For application in Oxygen Evolution Reaction catalysis, the samples NiFe-500 and NiFe-700 showed different overpotentials of 319 and 307 mV at 10 mA cm⁻². These low overpotential values indicate a higher electrochemical activity of the FCC Ni-Fe alloy and, for both samples, a superior electrocatalytic activity in comparison to RuO₂ e IrO₂ conventional catalysts. Furthermore, the samples showed high electrochemical stability in chrono potentiometric studies for up to 15 h. This current work highlights that the Ni-Fe alloys produced via the proteic sol–gel and with a reduction in H₂ methods can be promising for OER systems due to their good performance and low costs. Full article

Lignin obtained by hydrogenolysis of lignocellulose biomass is a prospective source of valuable green fuels and chemicals such as monophenols. One of the key factors in the chemical decomposition of lignin to monophenols is an efficient catalyst. Inert porous materials such as hypercrosslinked polymers are suitable catalytic supports for the immobilization of noble and transition metal nanoparticles. However, such polymers do not have acidic properties, which are crucial for catalyzing hydrolysis. In this work, we report novel, efficient catalysts for lignin hydrogenolysis to produce valuable monophenolic compounds. The synthesized catalysts contained Ni, Ru, and Ni–Ru nanoparticles supported on SiO₂-coated hypercrosslinked polystyrene (SiO₂@HPS). Ni-Ru/SiO₂@HPS demonstrated remarkable stability without any loss of the metallic phase and a high yield of monophenols (>42 wt.%) at close to full lignin conversion (>95 wt.%). This result was attributed to the synergy between the two metals and the support’s surface acidity. All catalysts were fully characterized by a series of physico-chemical methods. Full article

The paper introduces spatially stable Ni-supported bimetallic catalysts for CO₂ methanation. The catalysts are a combination of sintered nickel mesh or wool fibers and nanometal particles, such as Au, Pd, Re, or Ru. The preparation involves the nickel wool or mesh forming and sintering into a stable shape and then impregnating them with metal nanoparticles generated by a silica matrix digestion method. This procedure can be scaled up for commercial use. The catalyst candidates were analyzed using SEM, XRD, and EDXRF and tested in a fixed-bed flow reactor. The best results were obtained with the Ru/Ni-wool combination, which yields nearly 100% conversion at 248 °C, with the onset of reaction at 186 °C. When we tested this catalyst under inductive heating, the highest conversion was observed already at 194 °C. Full article